CN101733015B - Micro-porous membrane reinforced multi-layer fluorine-containing cross-linking ionic membrane and preparation method thereof - Google Patents

Micro-porous membrane reinforced multi-layer fluorine-containing cross-linking ionic membrane and preparation method thereof Download PDF

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CN101733015B
CN101733015B CN2009102311428A CN200910231142A CN101733015B CN 101733015 B CN101733015 B CN 101733015B CN 2009102311428 A CN2009102311428 A CN 2009102311428A CN 200910231142 A CN200910231142 A CN 200910231142A CN 101733015 B CN101733015 B CN 101733015B
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membrane
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microporous barrier
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CN101733015A (en
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张永明
唐军柯
刘萍
张恒
王军
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Shandong Dongyue Shenzhou New Material Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a micro-porous membrane compounded multi-layer perfluor cross-linking ionic membrane and belongs to the field of functional polymer compound material. The ion exchange membrane has a multilayer structure. A micro-porous membrane is compounded in the multilayer membrane to be used as reinforcement while a dual network structure containing the chemical bond cross linking and the physical bond of the high valence metallic compound and the acidic exchange group is arranged between the membrane forming molecules in the multilayer membrane. The ion exchange membrane prepared by the invention has higher high-temperature conductivity, higher dimensional stability and excellent mechanical strength.

Description

Fluorine-containing cross-linking ion membrane of a kind of microporous film enhanced multilayer and preparation method thereof
Technical field
The invention belongs to field of functional polymer composites, relate to the compound multi-layer perfluor cross-linking ion membrane of a kind of microporous barrier.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the TRT of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to PEM.
Now the perfluorinated sulfonic acid PEM that uses have good proton-conducting and chemical stability under (80 ℃) and the higher humidity at a lower temperature.But they also have a lot of defectives:, poor chemical stability not high as poor dimensional stability, mechanical strength etc.Film water absorption rate and size of causing because of suction under different humidity expand also different, and when film during at different operating mode down conversion, the size of film also will so change.So repeatedly, finally cause PEM generation mechanical damage.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and non-fluorin radical on these materials meeting attack film-forming resin molecules causes film generation chemical degradation and damaged, foaming.At last, when the operating temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃,, thereby the efficient of fuel cell is descended greatly because the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high operating temperature can improve the anti-carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane all has certain hydrogen or methanol permeability in addition, especially in DMFC, methanol permeability is very big, and this becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. and become the key subjects that fuel cell industries faces.
People have proposed certain methods and have solved these problems at present.Gore-Select series composite membrane liquid as the exploitation of W.L. Gore company adopts the porous teflon to fill the method (seeing US5547551, US5635041, US5599614) of Nafion ionic conductivity liquid, this film has higher proton conductive and bigger dimensional stability, but teflon creep at high temperature is very big, causes performance to descend.
Japan Patent JP-B-7-68377 proposed a kind of method, the porous media made from the proton exchange resins filled polyolefin, but its chemical durability deficiency, thereby aspect long-time stability existing problems.
Japan Patent JP-A-6-231779 has proposed another kind of Enhancement Method, is to use fluororesin fiber.The amberplex that it adopts the fluorocarbon polymer reinforcing material of fibrillation form to strengthen.But this method must add a large amount of relatively reinforcing materials, and in this case, the processing characteristics of film is tending towards difficulty, and the film resistance increase takes place possibly.
In the U.S. Pat 5834523 (Ballard company), the α of sulfonation, β, β-trifluorostyrene sulfonic acid and m-trifluoromethyl-α, β, methyl alcohol/the propanol solution of β-trifluorostyrene copolymer is immersed in the hole of porous PTFE film of swelling, dries under 50 ℃ of conditions then, obtains composite membrane.But need repeat polymer fully is filled in the hole of PTFE microporous barrier.
In WO98/51733, by hot pressing under 310 ℃ of vacuum states together the PTFE film of the film of the thick sulfuryl fluoride type of 25 μ m and Gore company.Then film hydrolysis in the KOH of dimethyl sulfoxide (DMSO) solution, make in the film-SO 2The F group changes into-SO 3 -At last being coated with three times mass concentrations in the one side of porous PTFE film is 5% sulfonate resin solution, makes film become as a whole in 150 ℃ of vacuum drying ovens.This method is too consuming time, and microporous barrier is difficult to be filled by sulfonate resin full.
And often there is phase-splitting in the compound perfluoro sulfonic acid membrane of perforated membrane between enhancing body and film-forming resin, also just have very big gap, thereby the film that causes being become has high gas permeability.
Crosslinking technological can improve the mechanical strength of the heat endurance of polymer, the swelling that reduces solvent, raising polymer, therefore has been widely used in fields such as separating absorption and various rubber elastomers.At present, for solving the existing problem of perfluorinated sulfonic acid PEM, explored and studied multiple crosslinking technological.
US20070031715 has described the cross-linking method of the crosslinked generation sulphonyl of sulfonic acid chloride acid anhydride, formed in the method sulphonyl acid anhydride cross-linked structure can improve the mechanical strength of film effectively, but this cross-linked structure has significant disadvantages: sulphonyl acid anhydride unit is unsettled to alkali.
US20030032739 then reaches crosslinked purpose by connecting at the alkyl between strand of the sulfonyl on the macromolecular chain.This crosslinked solvent swell that can reduce film well.But for obtaining not suitability for industrialized process of the required a lot of steps of this cross-linked structure.
US6733914 discloses the perfluor sulfonyl fluorine type film that will melt extrude and soaked the PEM that forms the sulfimide cross-linked structure in ammoniacal liquor, and the perfluoro sulfonic acid membrane of Chu Liing has good mechanical strength and dimensional stability like this.But utilizing the resulting film of this method will be uneven film, because ammonia enters film by the method for infiltration, ammonia meeting and sulfuryl fluoride react in the process of infiltration, the sulfuryl fluoride of reaction will stop the further diffusion of ammonia to film inside, thereby form very high crosslink density on the surface of film, and that the inside of film does not take place almost is crosslinked.The big crosslinked electrical conductivity of film that makes in surface sharply descends.
CN200710013624.7 and US7259208 disclose and have contained triazine ring cross-linked structure perfluoro sulfonic acid membrane, have excellent mechanical intensity and dimensional stability equally.
Chinese patent 200810138428.7 discloses the crosslinked and common enhanced multilayer perfluoro sulfonic acid membrane of microporous barrier of a kind of chemical bonding.Chemical bonding is crosslinked to carry out modification with the microporous barrier multiple means though used, and the performance of film is greatly improved on basis in the past, and film still exists film-forming resin to combine problems such as not firm with perforated membrane.
Only adopt the crosslinked film of chemical bonding, often can not form the very high degree of cross linking, to film to improve performance limited.Finally cause the performance of film can not reach the requirement of use.
But above each patent has only been improved the performance of an aspect of film, does not improve the dimensional stability of film and the electricity under the high temperature low humidity simultaneously and leads.
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: stable, high conductivity, high mechanical properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer descends, and (equivalent value EW value reduced, ion exchange capacity IEC=1000/EW), film strength also reduces simultaneously, and the also rising thereupon of the gas permeability of film, and this will produce very fuel cell and seriously influence.Therefore, the film that preparation has the macroion exchange capacity, have favorable mechanical mechanical strength and air-tightness, have a good stable is a fuel cell, and especially the fuel cell that uses on delivery vehicles such as automobile is able to practical key.
Summary of the invention
At the deficiencies in the prior art, the inventor after having paid creative work, thereby has finished the present invention through further investigation.
The invention provides the compound multi-layer perfluor cross-linking ion membrane of a kind of microporous barrier.It is characterized in that: described ionic membrane is to be the multilayer film of the 2-40 layer that forms of 600～1300 ion exchange fluoro resin by the EW value, preferred 2～5 layers, wherein having 1 layer at least, to have the chemical bonding cross-linked structure, have 1 tunic at least be the physical bond cross-linked structure that strengthens film, has at least 1 layer of acidic exchange group that has on high-valency metal compound and the described chemical bonding cross-linked structure to form as the micropore of reinforce with microporous barrier.
Described cross-linking ion membrane gross thickness 10～300 μ m are preferably 50～200 μ m, most preferably are 100～150 μ m.
Described chemical bonding cross-linked structure has and is selected from as shown in the formula (I), (II), (III), (IV) or one or more cross-bridge structures in the structure (V):
Figure G2009102311428D00031
Wherein, G 1=CF 2Or O, G 2=CF 2Or O, R fBe C 2-C 10Perfluor carbochain or chloride fluorocarbon chain;
Figure G2009102311428D00032
Wherein, R is methylene or perfluor methylene, and n is 0～10 integer;
Figure G2009102311428D00033
Described ion exchange fluoro resin be by tetrafluoroethene, one or more contain the perfluor alkene monomer of functional group and perfluor alkene monomer copolymerization that one or more contain crosslink sites forms, and also can be the mixtures of one or more above-mentioned copolymers.
The described fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (VI), (VII) or in the structure (VIII):
Figure G2009102311428D00034
R f3CF＝CF(CF 2) dY 2
(VII)
Figure G2009102311428D00041
Wherein, a, b, c are 0～5 integer, but can not be zero simultaneously;
N is 0 or 1; X is selected from F, Cl, Br or I;
D is 0～5 integer
R F1, R F2And R F3Be independently selected from perfluoroalkyl or dichlorodifluoromethan base;
Y 1, Y 2, Y 3Be independently selected from SO 2M, COOR 3Or PO (OR 4) (OR 5), wherein:
M is selected from Br, F, Cl, OR or NR 1R 2, wherein R is selected from methyl, ethyl, propyl group, H, Na, Li, K or ammonium root; R 1, and R 2Be selected from H, methyl, ethyl or propyl group respectively; R 3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R 4, R 5Be selected from H, Na, Li, K, ammonium root respectively, methyl, ethyl or propyl group.
The described fluorine-containing alkene monomer that contains crosslink sites can be general formula (IX) or (X) in one or both:
F 2C＝CFR f4Y 4
(IX)
Figure G2009102311428D00042
Wherein, Y 4, Y 5Be selected from Cl, Br, I or CN respectively;
A ', b ', c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0;
X 1Be selected from F, Cl, Br, I, SO 2F, SO 2Cl, SO 2Br or CN;
N ' is 0 or 1;
R F4, R F5, R F6Be selected from perfluoroalkyl or dichlorodifluoromethan base respectively.
Ion exchange fluoro resin of the present invention can be at microporous barrier surface-crosslinked, also can be crosslinked in the space of microporous barrier.
Described enhancing microporous barrier can be that organic micro film also can be inorganic microporous barrier, and the aperture is 0.1～1 μ m, and thickness is 5～100 μ m, is preferably 10～80 μ m, most preferably is 30～60 μ m; Porosity is 30%～99%, is preferably 50～80%.Organic micro film preferred polymers film wherein, special preferred fluorocarbon polymer film.More preferably, organic micro film is selected from eptfe film, silica modified porous hexafluoropropene film, porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer or porous polyimide film.Inorganic microporous barrier preferred microporous film ultra-thin ceramic film, ultra-thin molecular screen membrane, ultra-thin Si O 2Film, TiO 2Film, ZrO 2Film, Al 2O 3Film or cellular glass film etc.
Described microporous barrier preferably carries out surface silicon acidifying, sulfonation, sulphation, phosphorylation and/or hydrophilic modification.As concerning the fluorocarbon polymer film, can silicify to the surface, processing such as sulfonation, sulphation, phosphorylation.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorocarbon polymer film, comprises reduction modification method, laser emission modification method, plasma modification method and the silicic acid activation method of sodium naphthalene solution.Wherein preferred silicic acid activation method is because it can be at the silica that directly deposits water conservation on the fluorocarbon polymer film surface.By fluorocarbon polymer film surface after the modification hydrophilic group has been arranged, but preferably on this basis more further modification as with the fiber of modification at ethyl orthosilicate, ZrOCl 2-H 3PO 4Or further modification in the titanate esters etc.
For the surface modification of inorganic microporous barrier, then these inorganic microporous barriers directly can be positioned over ethyl orthosilicate, ZrOCl 2-H 3PO 4Or titanate esters, H 3PO 4, H 2SO 4Deng in carry out modification, also can when the synthesizing inorganic microporous barrier, add modifier directly to generate the modified inorganic microporous barrier, as phosphate and ethyl orthosilicate are mixed, become Modified Membrane with the alkali gel.The concrete grammar of for example silica modified voided polytetrafluoroethylene film is placed on SiCl with voided polytetrafluoroethylene film exactly 4Be warmed up to 110 ℃ in the atmosphere after 1 hour and kept 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified voided polytetrafluoroethylene film.
Titania modified cellular glass film method is for to place Ti (OEt) with the cellular glass film 4In/the water mixed system, stir adding concentrated ammonia liquor down, hydrolysis is left standstill and is obtained the cellular glass film that titanium dioxide is modified.
Also can be with inorganic ultrathin membrane such as TiO 2Film, ZrO 2Film is directly at H 3PO 4, H 2SO 4Deng soaking surface modification in the inorganic acid.
The method that also has a kind of modified inorganic ultrathin membrane of separating out jointly, be triethyl phosphate to be mixed with ethyl orthosilicate (1: 100 mass ratio) add entry and concentrated ammonia liquor, left standstill gel 12 hours, utilize surfactant such as hexadecyltrimethylammonium chloride to make the lamina membranacea gel then, obtain the ultra-thin silicon dioxide film of phosphoric acid modification.
Because perforated membrane carried out the surface active modification, have acidity or functional group and make and to form strong crosslinked action by the physical bond of high-valency metal compound between perforated membrane and the film-forming resin.
The metallic element of the metallic compound of the high valence state that described formation physical bond is crosslinked is selected from down one of column element or combination: W, Zr, Ir, Y, Mn, Ru, Ce, V, Zn, Ti or La element, these metallic compounds can account for perfluorinated ion exchange resin quality 0.001～5%, be preferably 0.01～4%, more preferably 0.1～3%, most preferably be 1～2%.
Described high volence metal ion compound can be selected from a kind of or combination double salt in nitrate, sulfate, carbonate, phosphate or the acetate of the highest price attitude of these metallic elements and middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or DMSO (dimethyl sulfoxide (DMSO)) complex compound of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state, comprises but is not only following Compound C e xTi (1-x)O 2(x=0.25～0.4), Ca 0.6La 0.27TiO 3, La (1-y)Ce yMnO 3(y=0.1～0.4), La 0.7Ce 0.15Ca 0.15MnO 3
Each layer in the described multi-layer perfluor amberplex can be in above-mentioned various resins one or more in select arbitrarily, but wherein have at least 1 layer of monofilm with microporous barrier as reinforce, last gained multilayer film must be the microporous barrier that contains cross-linked structure.
The present invention also provides the preparation method of described ionic membrane, comprises step:
(1) each layer in the fluorine-containing cross-linking ion membrane of microporous film enhanced multilayer can utilize the solution of perfluorinated ion exchange resin or fused mass by cast, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make, perhaps simultaneously and the microporous barrier composite membrane-forming;
(2) preparation of multilayer film is by compound the making of monofilm of preparation in (1), perhaps at monofilm or the basis that has made multilayer film utilize solution in (1) or fused mass by cast, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology make, equally can by multilayer film and monofilm or multilayer film and multilayer film is compound make;
(3) when needs add crosslinking agent and/or initator and high-valency metal compound, crosslinking agent and/or initator and high-valency metal compound add when carrying out step (1) and/or (2), perhaps crosslinking agent and/or initator and high-valency metal compound are scattered in the solvent to enter in the film by film mode of swelling in solvent;
(4) with step (2), the film that handle (3) is handled by the formation method of following arbitrary cross-linked structure; Form claim 3 described (I), (II), (III), (IV) and/or (V) shown in the cross-bridge structure.
The method that forms cross-bridge structure shown in the formula (I) is included in heat, light, electron radiation, plasma, X ray or radical initiator and exists down, also can when existing, one or more crosslinking agents form cross-linked structure by heat, light, electron radiation, plasma, X ray or action of free radical initiator.Wherein the structure of employed crosslinking agent is as shown in the formula shown in (XI):
X 2R f7X 3
(XI)
X 2, X 3Be selected from Cl, Br or I; R F7Be selected from perfluoroalkyl or dichlorodifluoromethan base.
Described radical initiator is organic peroxide or azo-initiator; Preferably, initator is an organic peroxide evocating agent; More preferably, initator is the perfluor organic peroxide.
Wherein the general formula of peroxide initiator can be expressed as (XII) and (XIII)
R 1OOR 2
(XII)
Figure G2009102311428D00061
R 1, R 2Can be respectively from following groups but be not limited only to choose these groups: H, C 1～C 20The C that alkyl or aryl replaces 1～C 20Alkyl, C 1～C 20Acyl group, C 1～C 20Aroyl, C 1～C 20Contain fluoroalkyl or perfluor C 1～C 20The C that alkyl or aryl replaces 1～C 20Alkyl, C 1～C 20Fluorine-containing acyl group or C 1～C 20Fluorine-containing acyl group, C 1～C 20Fluorine-containing aroyl or C 1～C 20The perfluor aroyl; But R 1, R 2Can not select H simultaneously.
R 3, R 4Can be respectively from following groups but be not limited only to choose these groups: C 1～C 20The C that alkyl or aryl replaces 1～C 20Alkyl, C 1～C 20The C that fluorine-containing or perfluoroalkyl or aryl replace 1～C 20Alkyl.
Azo-initiator is selected from: Celogen Az, azodiisobutyronitrile, AMBN, ABVN, azo-bis-iso-dimethyl, 1-((cyano group-1-Methylethyl) azo) formamide, 1,1 '-azo (cyclohexyl-1-cyano group), 2,2 '-azo (2-methyl-propyl amidine) dihydrochloride or 4,4 '-azo two (4-cyanopentanoic acid).
The method that forms (II), (III) cross-linked structure is: utilize sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide type resin and ammonia, hydrazine, organic diamine or can obtain through the substance reaction that chemical treatment discharges ammonia, hydrazine, organic diamine; Described organic diamine is C 1～C 20Alkyl or C 1～C 20Fluorine-containing alkyl diamine; Described organic or inorganic acid hydrochlorate, urea or the guanidine that can include but not limited to ammonia, hydrazine or organic diamine through the material that chemical treatment discharges ammonia, hydrazine, organic diamine;
The method that forms (IV) cross-linked structure is to utilize chlorosulfonic acid to handle the sulfonic fluoropolymer resin to obtain;
The method that forms (V) cross-linked structure is that the fluorine-containing sulfuryl fluoride resin in the sulfonic fluoropolymer resin in cyano-containing site, cyano-containing site, the sulfonic acid bromide resin that contains that contains sulfonic acid chloride resin or cyano-containing site in cyano-containing site form under hot or sour effect; Described acid is strong protonic acid or lewis acid; Wherein Bronsted acid for example can be selected from H 2SO 4, CF 3SO 3H or H 3PO 4Described lewis acid for example can be selected from ZnCl 2, FeCl 3, AlCl 3, organo-tin compound, organo-antimony compound or organic tellurium compound.
(5) product of step (4) is handled through alkali lye, acid solution according to this, thereby obtained the crosslinked exchange membrane containing fluorine that microporous barrier strengthens.
Described acid in the step (5) is hydrochloric acid, sulfuric acid or nitric acid; Described alkali is LiOH, NaOH or KOH; Described alkali lye and acid solution are the aqueous solution.
In above preparation method, when using casting, spin coating, curtain coating, silk-screen printing technique, spraying or impregnating technology constantly, solvent is but is not limited only to a kind of of following solvent or combination: one or more in dimethyl formamide, dimethylacetylamide, NMF, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerine.Solid masses content in the prepared resin solution is 1～80%, is preferably 5～70%, more preferably 10～60%, most preferably be 20～50%.Film-forming temperature is 30～300 ℃, is preferably 50～250 ℃, more preferably 100～200 ℃; Time is 10～100 minutes, more preferably 20～60 minutes.
In the compound multi-layer perfluor cross-linking ion membrane of microporous barrier of the present invention, by using means such as the crosslinked and high-valency metal compound of microporous barrier and chemical bonding and the physical bond of acidic exchange group formation be crosslinked, performance simultaneously acts synergistically, thereby has greatly improved the mechanical strength of ionic membrane.Particularly adopted the physical bond between high-valency metal compound and acidic exchange group crosslinked, has the very high degree of cross linking, and crosslinked between can realizing layer by layer, add as the amide group in the acid amides chemistry bonding cross-linking, triazine group in the triazine ring bonding cross-linking and can also form coordination, so just further improved the performance of film with the high-valency metal compound.Especially it is crosslinked to be stressed that microporous barrier that the surface had an acidic exchange base group modification forms physical bond by physical bond and high-valency metal compound and film-forming resin.So just solved the high problem of gas permeability of microporous barrier enhancing perfluoro sulfonic acid membrane traditionally.This may be because following reason: 1, surface-functionalized microporous barrier and film-forming resin adhesion are improved; 2, can form bonding structure with metallic compound because the surface of microporous barrier has functional group, this has further reduced the space between resin and microporous barrier.
The specific embodiment
By the following examples the present invention is further specified, but but it will be understood by those skilled in the art that these embodiments only are used to exemplify, but not spirit of the present invention and claimed scope are carried out any type of restriction.
Embodiment 1:
With repetitive be
Figure G2009102311428D00081
, the fluoropolymer resin of EW=1000 and carbonic acid vanadium (account for resin quality 0.01%) be distributed in propyl alcohol-water, makes total mass concentration and be propyl alcohol-aqueous solution of 5%, adds mass concentration then and be 5% peroxidating perfluor malonyl DMF solution, with surface H 3PO 4-SiO 2The eptfe film that 30 μ m of modification are thick (porosity is 70%) places above-mentioned solution to soak about 1 hour, and the film that will soak carries out drying on heating plate then, with rubber roll film is carried out roll extrusion therebetween., after 12 hours film is peeled off through 80 ℃ of vacuum drying, obtained having the ionic membrane (monofilm 1#) of cross-bridge structure for (I).Carry out hot pressing with above-mentioned two individual layer perfluor cross-linking ion membranes are stacked, make the double-deck microporous barrier of vanadium ion bonding and strengthen perfluor cross-linking ion membrane (multilayer film 1#).
Embodiment 2:
With repetitive be
Figure G2009102311428D00082
, EW=800 fluoropolymer resin extrude and obtain the film that thickness is 30 μ m, again with the thick silica modified porous hexafluoropropene film of 12 μ m 260 ℃ with vacuum state under hot pressing be in the same place, in 150 ℃ of vacuum drying ovens 1 hour then, be soaked in NH then 4In the DMF solution of Cl 5 hours, after the immersion, with film placed triethylamine 2 hours at 200 ℃, cross linking membrane.This film is handled with KOH solution, hydrochloric acid solution successively, obtained having the amberplex (monofilm 2#) of cross-bridge structure for (II).
With repetitive be
Figure G2009102311428D00083
, EW=1200 fluoropolymer resin and tetraphenyltin be extruded into the film that thickness is 20 μ m with double screw extruder, then with film 230 ℃ of down heating 10 hours, obtain the film of cross-bridge structure for (V).This film is obtained cross-linking ion membrane (monofilm 3#) with LiOH, salpeter solution processing successively.With monofilm 2#, overlapping, the hot pressing of 3#, and be immersed in the manganese nitrate solution 1 hour, and the crosslinked double-deck microporous barrier that obtains the manganese ion bonding strengthens amberplex (multilayer film 2#), and thickness is 62 μ m.
Embodiment 3:
With repetitive be
, EW=1100 fluoropolymer resin, lanthanum acetate (lanthanum acetate account for resin quality 0.001%) is dissolved in the solvent, makes total mass concentration and be 3% polymer resin solution, with the porous Al of surface phosphoric acidization 2O 3Film immerses in the above-mentioned solution, after 30 minutes film is taken out dry, then with this film through the 50KGy crosslinking with radiation, obtaining thickness is the ionic membrane (monofilm 4#) of the cross-bridge structure of 10 μ m for (I).
With repetitive be
Figure G2009102311428D00092
, EW=940 fluoropolymer resin, Ce (III)-DMSO complex compound (account for resin quality 0.1%) is dissolved among the DMSO, makes total mass concentration and be 30% DMSO solution, adds sulfuric acid-ZrO 2The polytetrafluoroethylene fibre of modification (diameter is 0.2 μ m, and length is 80 μ m, with the weight ratio of polymer be 7: 100) was handled 60 minutes down at 170 ℃ by the method for casting then, made the film that thickness is 10 μ m (monofilm 5#).
Carry out hot pressing with monofilm 4#, 4#, 5# perfluorinated sulfonic acid ionic membrane are stacked, the high volence metal ion bonding microporous barrier that obtains thickness 30 μ m strengthens three layers of cross-linking ion membrane (multilayer film 3#).
Embodiment 4:
With repetitive be
Figure G2009102311428D00093
, EW=700 Y (III) compound (account for resin quality 0.03%) of fluoropolymer resin, 18-hat-6 complexings be mixed among the DMF, make total mass concentration and be 20% solution, with the thick sulfuric acid-TiO of 10 μ m 2Modified porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer film places above-mentioned solution to soak about 1 hour, handled 10 minutes down at 120 ℃ then, obtaining thickness is the individual layer perfluorinated sulfonic acid ionic membrane of the microporous barrier enhancing of 10 μ m, and this amberplex being impregnated in get the cross-bridge structure in the chlorosulfonic acid then is the film (monofilm 6#) of formula (IV).
Above-mentioned ionic membrane is placed once more fluoropolymer resin, peroxidating perfluor bay two acyls, 1 of embodiment 1, soaked 0.5 hour in the DMF solution of 4-diiodo-octafluorobutane, then film is taken out dry, repeat above-mentioned soaking step, thereby film forming on the two sides, then film was handled 300 minutes down at 120 ℃, again gained film and monofilm 4# are hot pressed into metal ion bonding cross-linking four tunics (multilayer film 4#).
Embodiment 5:
With repetitive be
Figure G2009102311428D00101
, EW=1300 fluoropolymer resin, acetylacetone,2,4-pentanedione-Ce (III) complex compound (addition be resin quality 0.01%), AMBN, 1,4-diiodo-octafluorobutane is dissolved among the DMF, with the ZrO of phosphoric acid modification 2Microporous barrier (porosity is 80%, and thickness is 20 μ m) soaked 30 minutes in this solution, handled 60 down at 170 ℃ then, made the film that thickness is 20 μ m.Again the perfluorinated sulfonic resin among the embodiment 4 is mixed in the N-methyl pyrrolidone and obtains solution, using this solution to become thickness in the spin coating of the both sides of above-mentioned film is the film of 30 μ m, prepares three layers of perfluorinated ion-exchange membrane (multilayer film 5#).Film was handled 2.4 hours down at 69 ℃, and the cross-bridge structure that obtains three layers of metal ion bondings is the perfluoro sulfonic acid membrane of formula (I).
Above-mentioned ionic membrane is placed above-mentioned fluoropolymer resin, AMBN, 1 once more, 4-diiodo-octafluorobutane, DMF-Ce (III) complex compound are dissolved in the solution that obtains among the DMF, soaked 0.5 hour, then film is taken out dry, repeat above-mentioned soaking step, thereby film forming on the two sides is handled film 300 minutes down at 120 ℃ then, obtains five layers of microporous barrier of metal ion bonding and strengthens perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 6#).
Multilayer film 5#, 6# are carried out hot pressing, and eight layers of microporous barrier that make the metal ion bonding strengthen perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 7#).
Embodiment 6:
With repetitive be
Figure G2009102311428D00102
, EW=1300 fluoropolymer resin and La (1-y)Ce yMnO 3(account for resin quality 0.01%) is scattered in the hempa acid amide, by spraying coating process method in a vacuum, is sprayed on sulfuric acid modified ZrO 2Microporous barrier (porosity is 80%, and thickness is 20 μ m) obtains the film that thickness is 20 μ m.Film was handled 100 minutes down at 230 ℃, and obtaining the cross-bridge structure is the individual layer perfluoro sulfonic acid membrane (monofilm 7#) of formula (I).
Use above-mentioned solution, pass through the spraying coating process method once more in the both sides of monofilm 7#, making thickness is three layers of crosslinked perfluoro sulfonic acid membrane of 60 μ m.At its both sides hot pressing monofilm 7#, make microporous barrier and strengthen crosslinked five layers of perfluoro sulfonic acid membrane (multilayer film 8#).
Embodiment 7:
With repetitive be
Figure G2009102311428D00111
, EW=1300 fluoropolymer resin, La (OH) 3(account for resin quality 0.5%), benzoyl peroxide, 1,14-diiodo-20 fluorine ten alkane are dissolved in the dimethyl sulfoxide (DMSO), thick and porosity is that 60% improved silica microporous barrier is immersed in the above-mentioned solution with phosphate and the cogelled 30 μ m that obtain of esters of silicon acis again, after the immersion, film was handled 3 minutes down at 160 ℃, obtaining crosslinked thickness is the inorganic microporous barrier enhancing perfluoro sulfonic acid membrane (monofilm 8#) of 30 μ m.
Above-mentioned ionic membrane is placed the same fluoropolymer resin of formula, zeolite, benzoyl peroxide, 1 once more, soaked in the dimethyl sulphoxide solution of 14-diiodo-20 fluorine ten alkane 0.5 hour, then film is taken out dryly, repeat above-mentioned soaking step, thus on the two sides film forming.Then film was handled 300 minutes down at 120 ℃, obtained three layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 9#).
Carry out hot pressing with three multilayer film 9# are stacked, nine layers of microporous barrier that make enhancing strengthen perfluorinated sulfonic acid cross-linking ion membranes (multilayer film 10#).
Embodiment 8:
With repetitive be
Figure G2009102311428D00112
, the EW=1250 fluoropolymer resin, pyridine-Ru complex solution (account for resin quality 0.63%), CsH 2PO 4(resin and CsH 2PO 4Mass ratio be 100: 20) fully mix, be dissolved into then in the hempa acid amide, obtain total mass concentration and be 30% solution, with the thick and porosity of 10 μ m is that porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer film of 89% places above-mentioned solution to soak about 1 hour, obtains the film that thickness is 10 μ m.Film was handled 100 minutes down at 230 ℃, obtained crosslinked individual layer micropore and strengthen perfluoro sulfonic acid membrane (monofilm 9#).
Use above-mentioned solution, pass through the spraying coating process method once more in the both sides of monofilm 9#, making thickness is three layers of crosslinked perfluoro sulfonic acid membrane of 60 μ μ m.At its both sides hot pressing monofilm 9#, make crosslinked five layers of microporous barrier and strengthen perfluoro sulfonic acid membrane (multilayer film 11#).
Embodiment 9:
With repetitive be
Figure G2009102311428D00113
, the fluoropolymer resin of EW=900 and porosity that thickness is 30 μ m be 50% expander polytetrafluoroethylene (PTFE) hot pressing film forming, is immersed in NH then 3DMF solution in 5 hours, after the immersion, handle down film at 200 ℃ with (II) cross-bridge structure.After this film alkali lye, acid solution processing, the DMF solution that is immersed in acetylacetone,2,4-pentanedione-Ir (III) obtains the cross linking membrane of metal ion bonding (monofilm 10#).
With repeat unit structure be
, EW=1200 fluoropolymer resin, tetraphenyltin mixes with double screw extruder, and then with thickness be that 50 μ m and porosity are 80% TiO 2Microporous barrier hot pressing is compound, then film is heated 10 hours the film with (V) cross-bridge structure down at 230 ℃.This film being placed mass concentration is 35% hydrazine hydrate 10 hours again, take out back heating 5 hours, (V) cross-bridge structure and (III) film of cross-bridge structure are arranged simultaneously, after this film is handled with alkali lye, acid solution, film is immersed in the nitric acid ruthenium 2 hours, obtains the cross linking membrane (monofilm 11#) of ruthenium ion bonding.
With monofilm 10#, 11# and multilayer film 11# and the overlapping hot pressing of multilayer film 7# film, obtain crosslinked microporous barrier and strengthen 15 tunics (multilayer film 12#), thickness is 220 μ m
Embodiment 10:
With repetitive be
Figure G2009102311428D00122
, EW=700 fluoropolymer resin, repetitive is
Figure G2009102311428D00123
The fluoropolymer resin of EW=1300 (two kinds of resin quality ratios are 1: 0.2), nitogen-contained crown ether-Ce complex compound (account for total resin quality 1%) and AMBN mixed dissolution are in DMF, make total mass concentration and be 20% solution, be that 50 μ m and porosity are that 75% micropore glass film film places above-mentioned solution to soak about 3 hours then with thickness, soak the back heating and obtain the monofilm that contains (I) cross-bridge structure that thickness is 50 μ m, again this amberplex is put in the chlorosulfonic acid, is had the film (monofilm 12#) of (IV) cross-bridge structure.
With monofilm 12# and multilayer film 2# hot pressing, three layers of perfluorinated sulfonic acid microporous barrier that make the metal ion bonding strengthen cross-linking ion membrane (multilayer film 13#).
Embodiment 11:
With repetitive be
Figure G2009102311428D00131
, EW=1200 fluoropolymer resin, Mn (OH) 3(account for resin quality 2%) and triphenyl tin hydroxide are scattered among the DMF, place above-mentioned solution to soak half an hour approximately the thick porous polyimide film of 20 μ m, handled 60 minutes down at 170 ℃, making thickness is the film with (V) cross-bridge structure of 20 μ m.The perfluorinated sulfonic resin among the embodiment 4 is mixed in the N-methyl pyrrolidone again and obtains solution, using this solution to become thickness in the spin coating of the both sides of above-mentioned film then is the film of 30 μ m, prepares three layers of micropore and strengthens perfluorinated ion-exchange membrane.Film was handled 2.4 hours down at 190 ℃, and three layers of crosslinked microporous barrier that obtain the manganese ion bonding strengthen perfluoro sulfonic acid membrane (multilayer film 14#).
Embodiment 12:
With repetitive be
, EW=1200 fluoropolymer resin prepare monofilm with the method that melt extrudes, then this film was at high temperature handled 3 hours, obtaining the cross-bridge structure is the monofilm 13# of formula (II).Fold multilayer film 3# on the two sides of monofilm 13#, and 120 ℃ of hot-pressing processing, hydrolysis acidification obtains seven layers of cross-linked perfluorinated sulfonic acid microporous barrier and strengthens films (multilayer film 15#) then.
Embodiment 13:
With repetitive be
Figure G2009102311428D00133
Fluoropolymer resin, after cyclodextrin-W (III) complex compound (account for resin quality 0.034%) mixes, be scattered in the N-methyl pyrrolidone that to form solid masses content be 30% dispersion liquid, with the thick and porosity of 10 μ m is that 65% expanded ptfe film places above-mentioned solution to soak half an hour approximately, soaks the back at 190 ℃ of film forming (monofilm 15#).
With above-mentioned fluoropolymer resin be with repetitive
Figure G2009102311428D00141
Fluoropolymer resin be after 1: 5 ratio is mixed in mass ratio, be distributed among the DMSO, after adding a spot of organo-antimony compound catalyst, handle the film (monofilm 16#) that formation has triazine crosslinked bridge cross-linked structure down at 230 ℃ by the The tape casting film forming and with film.
Monofilm 16# and monofilm 15# are stacked alternately until 5 layers, and hot pressing is compound then, and obtaining thickness is five tunics (multilayer film 17#) of 50 μ m.
Comparative example 14:
With repetitive be
Figure G2009102311428D00142
, EW=1100 fluoropolymer resin be distributed in the solvent, make total mass concentration and be 3% polymer solution, with porous Al 2O 3Film immerses in the above-mentioned solution, soak after 30 minutes film is taken out dry, then with this film through the 50KGy crosslinking with radiation, obtaining thickness is that 20 μ m have the ionic membrane (monofilm 4#) of cross-bridge structure for (I).
With repetitive be
Figure G2009102311428D00143
, EW=940 fluoropolymer resin be distributed among the DMSO, make mass concentration and be 30% DMSO solution, handled 60 minutes down at 170 ℃ by the method for casting, make the film that thickness is 10 μ m (monofilm 5#).
Carry out hot pressing with monofilm 2#, 4#, 5# perfluorinated sulfonic acid ionic membrane are stacked, then with multilayer film 2# hot pressing, the microporous barrier that obtains thickness and be 124 μ m strengthens four layers of cross-linking ion membrane (multilayer film 18#).
Comparative example 15:
Service property (quality) concentration is 10% nafion
Figure G2009102311428D00144
Solution, the eptfe film that 30 μ m are thick (porosity is 70%) place above-mentioned solution to soak about 1 hour, and the film that will soak carries out the drying processing on 170 ℃ of heating plates then, obtain the thick microporous barrier of 30 μ m and strengthen amberplex.
Embodiment 23
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1,95 ℃ of electrical conductivity of the multi-layer perfluor cross-linking ion membrane that microporous barrier is compound, hot strength, hydrogen permeate electric current, performances such as size changing rate all are better than the fluorine-containing cross-linking ion membrane of microporous film enhanced multilayer, and improving of highly significant especially arranged aspect gas permeation resistance.
The various films of table 1 characterize
Figure G2009102311428D00161

Claims (4)

1. multi-layer perfluor cross-linking ion membrane that microporous barrier is compound, be to be the multilayer film of the 2-40 layer that forms of 600～1300 perfluorinated ion exchange resin by the EW value, it is characterized in that: having 1 layer in the described ionic membrane at least, to have the chemical bonding cross-linked structure, have 1 tunic at least be the physical bond cross-linked structure that strengthens film, has at least 1 layer of acidic exchange group that has on high-valency metal compound and the described chemical bonding cross-linked structure to form as the micropore of reinforce with microporous barrier;
Described chemical bonding cross-linked structure have be selected from following formula (I), (II), (III), (IV) or (V) shown in structure in one or more cross-bridge structures:
Figure FSB00000425851800011
Wherein, G 1=CF 2Or O, G 2=CF 2Or O, R fBe C 2-C 10Perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is 0～10 integer;
Figure FSB00000425851800013
The metallic element of described high-valency metal compound is selected from down one of column element or combination: W, Zr, Ir, Y, Ru, Ce, V, Zn, Ti or La element; And
Described high-valency metal compound is selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, EDTA, DMF or the DMSO complex compound of middle valence state;
Or be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state; Described oxide with perovskite structure is Ce xTi (1-x)O 2, Ca 0.6La 0.27TiO 3, La (1-y)Ce yMnO 3Or La 0.7Ce 0.15Ca 0.15MnO 3, wherein x=0.25～0.4, y=0.1～0.4.
2. ionic membrane as claimed in claim 1 is characterized in that: this multi-layer perfluor cross-linking ion membrane is to be the multilayer film of the 2-5 layer that forms of 600～1300 perfluorinated ion exchange resin by the EW value.
3. ionic membrane as claimed in claim 1 is characterized in that: described microporous barrier is selected from eptfe film, expanded microporous polytetra fluoroethylene-EPTEE-hexafluoropropene film, porous polyimide film, SiO 2Film, TiO 2Film, ZrO 2Film, Al 2O 3Film or cellular glass film.
4. ionic membrane as claimed in claim 1 is characterized in that: described crown ether is a nitogen-contained crown ether.
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